Stability of Adsorbed Water on TiO2–TiN Interfaces. A First-Principles and Ab Initio Thermodynamics Investigation

Titanium nitride (TiN) surfaces can oxidize, and the growth of a TiOx layer on the surface along with the likely presence of water in the surrounding environment can modify the properties of this widely used coating material. The present density functional theory study, including Hubbard + U correction (DFT+U), investigates the stability of adsorbed water at TiO2–TiN interfaces with different defects that serve as a model for an oxide layer grown on a TiN surface. Surface free energy calculations show the stability of a perfect TiN–TiO2 interface at regular O pressures, while oxygen vacancy-rich TiO1.88–TiN is more favorable at reducing conditions. An isolated water is preferentially adsorbed dissociatively at perfect and oxygen-defective interfaces, while molecular adsorption is more stable at higher coverages. The adsorption energy is stronger at the oxygen-defective interfaces which arise from the high concentration of reduced Ti3+ and strong interfacial atomic relaxations. Ab initio atomistic thermody...